Safety in Sulfuric Acid

Storage Tanks
Commonly used in the CPI, sulfuric acid requires many special precautions to ensure
its safe handling and storage
Koya Venkata
Reddy
FACT Engineering and
Design Org. (FEDO)

IN BRIEF
CORROSION CONTROL
INSPECTION
INSTRUMENTATION
SWITCHING OF TANK
SERVICE
TANKS IN SPENT-ACID
SERVICE
SECONDARY
CONTAINMENT SYSTEMS
PPE AND HSE
VENTING REQUIREMENTS
TRANSFER PUMPS
HOT WORKS IN TANK
FARMS
PIPELINES, HOSES AND
VALVES

44

ulfuric acid, sometimes called the

king of all chemicals, is widely used
in the chemical process industries
(CPI) for the manufacture of various fertilizers and other chemicals. Sulfuric
acid (H2SO4) is typically stored and handled
in steel storage tanks in tank farms (Figure
1) located at ports, sulfuric acid plants, fertilizer plants and so on. Numerous incidents
involving explosions and spills in sulfuric acid
storage tanks have been reported worldwide. All too often, a lack of understanding
regarding the proper safety aspects required
for handling and storing sulfuric acid leads to
catastrophic accidents. These incidents can
result in environmental pollution, as well as
injuries and fatalities.
For example, in 2001 at a petroleum refinery in Delaware, a crew of contractors was
repairing grating on a catwalk in a sulfuric
acid storage-tank farm when a spark from
their hot work ignited flammable vapors in
one of the storage tanks. One of the acid
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FIGURE 1. Storage tanks in sulfuric acid serice require many

special precautions to ensure safe operations and prevent
accidental spills or ignitions

storage tanks separated from its floor, instantaneously releasing its contents. Other tanks
in the tank farm also released their contents.
A fire burned for approximately 30 min, and
sulfuric acid reached a nearby river, resulting in significant environmental damage. One
worker was killed and eight were injured [1].
Such incidents draw attention to the vulnerability of sulfuric acid storage tanks to
fires and explosions, in addition to accidental
spillage. These occurrences can be avoided
by understanding the various aspects of corrosion in storage tanks, inspection and venting requirements, spillage-containment systems, instrumentation, proper materials of
construction, various governing codes and
standards, guidelines for hot work and so
on. This article describes various problems
faced in sulfuric acid tanks and the efforts
needed to mitigate them.
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Corrosion control

Inspection

Corrosion is one of the most prevalent issues in handling sulfuric acid. Two common
corrosion mechanisms hydrogen grooving and boundary-layer corrosion are
especially dangerous in sulfuric acid service
because they lead to the formation of hydrogen gas (H2), which is highly flammable,
colorless, odorless and readily ignitable. It
forms an explosive mixture with air and oxygen. The lower and upper explosive limits
(LEL and UEL) of H2 are 4% and 74.2%, respectively. This means that if the concentration of H2 is between 4% and 74.2%, and if
the gas mixture is ignited, it will lead to an
explosion, causing potentially fatal harm and
damage to assets. Hydrogen grooving and
boundary-layer corrosion are detailed in the
following sections.
Hydrogen grooving. Tanks for storing concentrated sulfuric acid typically are made
of carbon steel. The acid reacts with iron
(Fe) in the shell, forming a protective layer
of ferrous sulfate (FeSO4), while simultaneously releasing H2, according to the
following reaction:

Periodic
thickness 98% sulfuric acid
measurements of a
tanks shell and roof
should be carried out
S03 absorber
to ascertain whether Oleum
the tank is fit for service. According to the
recommendations of
the National Association of Corrosion
Engineers
(NACE;
Houston; www.nace.
org) Standard RP
0294-94, an internal
inspection of sulfuric
acid tanks is to occur
every five years, and
an external in-service inspection is to be
carried out every two years [2]. Similarly, the
American Petroleum Institute (API) Standard
653 requires the evaluation of flaws, deterioration or other conditions that might affect the
performance of a tank and the determination
of its suitability for the intended service [3].
The periodic inspections should be performed more frequently as tanks become
older. Per NACE RP 0294-94, inspection
frequencies may be decided on the basis of
operating conditions, experience, inspection
results, fitness-for-service evaluations and
risk analysis [2]. Furthermore, risk-based inspection (RBI) is to be conducted for all tanks
in addition to inspections at service intervals.
Historic tank leakage and failure data are integral to RBI assessments.

Fe + H2SO4 FeSO4 + H2
At the inlet line, as the acid is flowing into
the tank, H2 bubbles float up and come into
contact with the metal. The bubbles will
scrape off the iron sulfate coating, exposing
bare metal. This will form more iron sulfate
and release more H2 bubbles. Eventually, the
formation of H2 bubbles in the metal forms
grooves or corroded portions and is called
hydrogen grooving.
Boundary layer corrosion. In tank farms, a
corrosive atmosphere also prevails, as sulfur
dioxide vapors from the storage tanks can
combine with moisture, forming sulfurous
acid (H2SO3). This causes the tank roofs
and other iron-containing materials in the vicinity to corrode.
In acid plants, the sump tanks of absorption towers contain acid analyzers that control the addition of dilute acid. If these analyzers malfunction, it can lead to an increase
in the acid temperature. If high-temperature
acid is transferred to carbon-steel storage tanks, corrosion will occur at a much
faster rate.
The general rate of shell corrosion of storage tanks for concentrated sulfuric acid service is approximately 5 to 20 mils per year
(0.005 to 0.020 in./yr) [1]. Anodic protection
should be provided for the storage tanks to
minimize the corrosion of the shell.
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LT

Oleum storage tank

FIGURE 2. Oleum, a product

of sulfuric acid plants, creates
safety issues in storage tanks
due to the presence of sulfur
trioxide (SO3) fumes

Instrumentation
As previously stated, sulfuric acid spills can
be extremely dangerous. Therefore, level
measurement and control in storage tanks in
sulfuric acid service is of the utmost importance. First and foremost, all tanks should
be provided with a level indicator. Additionally, high- and low-level switches should be
provided on tanks to contain the overspill
control and to avoid vacuum conditions
when pumps are transferring acid to consuming plants. All instruments are expected
to be compliant with safety integrity level
(SIL) 2. For more information on SIL classifications, see Tolerable Risk, Chem. Eng.,
Sept. 2007, pp. 6974.
For acid storage tanks, the use of radartype level-measurement devices is recommended, along with control-room alarms.
However, many facilities have installed differential-pressure (DP) level-measurement
devices without any reported issues. The

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FIGURE 3. A metal catwalk on the roof of

a storage tank provides some protection
for workers, as it is unsafe for personnel
to walk directly on a tanks shell

wetted parts of radar level gages should

be 316 stainless steel, Alloy 20 or
Teflon-lined.
Some older tank farms use a type of
tank level-measurement device called
a bubbler system, which uses instrument air as its medium. A small flow of
instrument air (forming bubbles) enters
the tank near its floor through the level
probe. The air introduces some turbulence into the acid near the wall of the
tank, which increases the corrosion
rate by disturbing the protective FeSO4
layer. Instrument air also contains moisture and oxygen, much of which would
likely be absorbed soon after coming
into contact with the acid solution [1].
Hence, level measurements based on
bubbler systems are to be avoided in
sulfuric acid storage tanks, especially in
spent-acid service, as air can form an
explosive mixture with the volatile hydrocarbons present in the acid.
Flow measurement is also an integral
part of sulfuric acid handling. Magnetic
flowmeters, Coriolis mass flowmeters,
rotameters or ultrasonic flowmeters may
be used to measure the flow of acid
into and out of tanks. As with level instruments, all flow instruments are to
be SIL 2 compliant.

Switching of tank service

Some tanks must handle various forms
of sulfuric acid, and switching between
these materials introduces increased
risk. For instance, in some tank farms,
tanks must be emptied to switch material-handling service between oleum
(an intermediate in sulfuric acid production) and sulfuric acid or between concentrated sulfuric acid and dilute spent
acid. These switchovers do not typically
require cleaning or draining, simply the
removal of as much material as possible
via pump. Each switchover represents an
opportunity to exacerbate corrosion and
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potentially release sulfur trioxide (SO3) vapors or volatile hydrocarbon vapors.

Operators must be attentive and
cautious with tanks in oleum service.
Oleum is sulfuric acid (100%) containing
around 23% free SO3. In some sulfuric
acid plants, oleum is also produced by
absorbing SO3 in concentrated sulfuric
acid, and it is common practice to locate
the oleum tanks near sulfuric acid tanks.
When oleum is introduced in a storage
tank, SO3 fumes are emitted out of the
vent, creating visible pollution and a corrosive atmosphere. To curb the SO3
fumes, small-diameter packed columns
filled with random packings (Intallox Saddles are recommended) are fitted on top
of storage tanks, as shown in Figure 2. A
bleed of sulfuric acid (98%) is taken from
the transfer-pump discharge and fed to
the top of the packed column to absorb
the rising SO3 fumes from the tank. After
absorbing SO3 fumes, the concentrated
sulfuric acid is self-drained into the tank.

Tanks in spent-acid service

Fresh sulfuric acid typically contains
98.4% acid and 1.6% water. Spent acid
typically contains 8895% acid and up to
5% water, with the balance consisting of
hydrocarbons, including some light hydrocarbons that can vaporize. A spentacid storage tank should be designed
and operated as if it contained volatile
hydrocarbons [4].
Special precautions are to be taken
in storing spent sulfuric acid in storage
tanks. The spent acid comes from various process industries as a byproduct
and contains volatile hydrocarbons,
which can be released during temperature variations in the atmosphere (thermal
breathing). Therefore, blanketing of the
storage tanks with an inert gas, such as
carbon dioxide or nitrogen is advisable.
Also, vent valves are to be provided with
emergency tank venting and must be
sized for the worst case, taking precautions for scenarios such as a failure of the
inerting system (allowing excessive flow
of inert gas to enter the tank) or an external fire that volatilizes hydrocarbon liquids
in the tank. Additionally, flame arrestors
should be placed in the vent line.
Tanks in spent-acid service should be
provided with a frangible roof [1]. A frangible roof is a weak roof-to-shell attachment that preferentially fails over other
welded joints when subject to overpressure. Failure of the roof-to-shell joint pro-

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FIGURE 4. Proper care must be taken when executing hot FIGURE 5. The same tank from Figure 4 was badly damaged after its roof exploded due to hot work
works in the presence of sulfuric acid storage tanks
on the roof and the formation of hydrogen gas inside the tank while the tank was in service

vides a means to relieve overpressure

and to avoid catastrophic failure of the
tank and loss of its contents.

Secondary containment systems

Special measures can be taken to ensure that no acid escapes to the environment in the form of secondary containment systems, including the installation
of dikes. Dikes are to be built to contain
110% of the largest storage-tank capacity to contain the accidental overspill or
catastrophic failure of the tanks. Dikes
must also be designed to withstand not
only the hydrostatic load of the liquid in
the tank, but also for the dynamic tidalwave effect of liquid-flow load in the case
of tank failure. Acid-proof brick lining is to
be laid inside the dike so that spilled acid
does not permeate into groundwater. In
addition to NACE RP 294-94 and API
653, API Standards 650 and 620 also
provide helpful guidance in the construction of sulfuric acid storage tanks.
Although dikes can be an extremely
helpful measure in protection against
tank spills and failures, precaution must
be taken when handling the rainwater
that collects inside the dike area to prevent environmental contamination. Collected water from dikes in sulfuric acid
service is acidic in nature because of
the probable leaks of gases from vents
inside the dike. This can create environmental issues if released to water bodies without correcting for pH. All rainwater that accumulates inside the dike area
should be collected and tested for pH. If
required, the pH should be adjusted to
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ensure it is within the acceptable range,

typically 6.5 to 8.5.
Suitable valves must be placed at the
dike wall so as to divert the clean rainwater to the dedicated rainwater drain
and contaminated rainwater to an effluent treatment plant (ETP). Any accidentally spilled acid is to be collected in spill
tanks and neutralized properly before
disposal in the ETP.

PPE and HSE

Although sulfuric acid itself is not flammable, it should not be stored near
organic materials, nitrates, carbides,
chlorates or metal powders. Contact
between high concentrations of sulfuric
acid and these materials may cause ignition. Proper personal protective equipment (PPE) and health, safety and environmental (HSE) precautions are critical
in any facility that handles sulfuric acid.
Some best practices for PPE and HSE in
sulfuric acid handling are as follows:
1. Suitable eye-wash stations should
be located near the tank farm for the
safety of personnel. The eye washers
are to be tested for their functionality
every shift.
2. All of the flanges in the lines are to be
covered with lead cladding to protect
the operating personnel from accidental acid leaks.
3. Metal catwalks should be provided
for working on top of tanks. Operating personnel should always use the
catwalk and never walk directly on the
tank shell (Figure 3).
4. All lines should be sloped toward the

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TABLE 1. GUIDELINES FOR VALVES IN SULFURIC ACID SERVICE

All of the valves in acid tank farms are to be constructed of Alloy 20
Ball valves or plug valves are to be used for isolation purposes
Copper, brass and bronze valves are not acceptable for sulfuric acid service at any concentration

TABLE 2. CRITERIA FOR MATERIALS OF CONSTRUCTION FOR PIPING IN SULFURIC ACID

SERVICE
Fluid velocity (m/s)

Material of construction

Temperature limits, C

01

Carbon steel

Ambient

02.5

SS 316

Ambient

07

Alloy 20

60

For all ranges

Teflon-lined pipe

200

storage tank, or toward the point of

consumption. This will prevent the
accumulation of acid in low points in
the line, thereby eliminating possible
safety hazards.
5. Operating personnel should wear
gloves that are loose enough to
be easily removed in case acid
enters them.
6. Helmets should be worn at all times. To
ensure eye and face protection, a full
face shield and safety goggles are also
necessary. Goggles and a face shield
are especially crucial when working in
a place where splashes can occur unexpectedly. It is essential that eye protection is provided from all angles.
7. In the event of a small spill, one
should contain and neutralize the acid
with lime.
8. Whenever a modification is carried
out in the storage tank area, a hazard
and operability (HAZOP) study should
be conducted before proceeding to
implementation.

Venting requirements
Another crucial aspect to ensuring storage-tank safety is adequate venting.
Some best practices associated with tank
venting are as follows:
1. Each sulfuric acid storage tank should
be provided with an individual breather
valve. The vent diameter is to be calculated based on in-breathing, out-breathing and thermal-breathing requirements
according to API Standard 2000 [5].
2. The vent area should be greater than
the sum of the inlet-, outlet- and drainline areas.
3. The vent (breather) valve should be
kept at the top of the tank. At no instance should it be located at ground
level, as it has the potential for inundation in the case of tank rupture or the
dike filling with acid or stormwater.
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4. If acid switchover (between either oleum

and sulfuric acid or concentrated sulfuric acid and dilute spent acid) is routine practice in the tank farm, the vent
valves must be sized for the worst-case
scenario of vapor release.
5. After decommissioning, the tank
should be re-commissioned by introducing acid very slowly, so as to avoid
static electricity.
6. The structural integrity of storage-tank roofs is to be inspected
in detail.
7. An explosion-proof hatch cover (minimum of 600 mm in size) should be provided on the tank roof.

Transfer pumps
Transfer pumps are used to transfer sulfuric acid from the tank farm to the endproduct processing plant or consuming
plants (for example, a fertilizer plant), where
acid is fed into chemical reactors. Careful
attention must be paid to these pumps.
Some recommendations for sound transfer-pump operations are as follows:
1. The transfer pumps to the consuming
plants shall have a low-level tank trip.
2. The discharge line should be provided with a pressure gage and nonreturn valve.
3. For the transfer of sulfuric acid from
ships at a higher rate, the discharge
line should have an excess-flow check
valve to prevent accidental spillage of
acid to the surrounding environment or
to bodies of water.

Hot works in tank farms

Hot works those tasks that require the
use of flames or very high temperatures,
such as welding and steel-cutting must
be completed with safety in mind. This is
especially crucial in tank farms. The following are some guidelines for executing
hot-works tasks in facilities where sulfuric
acid is being stored:
1. Hot work is to be permitted only after
measuring for flammable gases in the
storage tank area. The measurement
of flammable gases in the storage tank
area is to be done continually during
the hot work period.
2. According to API RP 2009, in situations where the work is delayed or suspended in an area that has previously
been pronounced gas-free, the permit
system should specify the length of time
beyond which oxygen and flammability
detector tests must be repeated or the

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permit reissued [6].

3. Periodic combustible-gas and oxygen
retests (or continuous monitoring) may
be required while hot work is proceeding. The permit should specify the
monitoring frequency.
4. If the hot work is to be performed on
the shell or roof of the storage tank,
and if there are holes in the roof or
shell, the tank contents must be emptied and purged with inert gas prior to
the hot work.
In many instances, non-compliance with
the above measures is a main cause for
explosions in sulfuric acid tanks. Figures
4 and 5 illustrate the devastation caused
by not taking the proper precautions with
hot-works tasks. Figure 4 shows a storage tank in sulfuric acid service. Figure 5
shows the same tank after a catastrophic
explosion due to the formation of H2 gas
during hot work.

Pipelines, hoses and valves

Many special design and operating considerations should be taken for piping,
hoses and valves that are to handle sulfuric acid. Table 1 provides some best
practices for valves in sulfuric acid service. For acid-transfer lines, the pipeline
should be of one piping class higher than
required to mitigate the risk of accidental
rupture or overpressurization.
The materials of construction for piping are dependent on fluid-flow velocities
and quality concerns. If iron contamination is a concern for the process, as in
the manufacture of caprolactam, carbon
steel is to be avoided. Polyvinyl chloride
(PVC) and chlorinated PVC are only to
be used for vent lines and overflow lines.
These pipes should not be used for liquid
service. Table 2 provides some criteria for
piping materials of construction based on
velocity and temperature requirements.
In general, piping should be inspected
visually every year. Ultrasonic thickness
tests should occur biennially. Depending on the actual plant experience, an
increase or decrease in the schedule of
inspection may be required. Extra attention should be paid to elbows, tees,
valves and any other areas in the piping
where flow disturbances (and erosion or
corrosion) could occur. Piping inspection criteria from API 570 may be used
for guidance [7].
A hose lined with polytetrafluoroethylene (PTFE) is acceptable for 9398%
sulfuric acid service. The hose should
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be designed with a minimum working pressure of 14 kg/cm2 and be fullvacuum rated. The end fittings must
be crimped or swaged. Banding is
not recommended. The hose-end fittings should be 316 stainless steel with
flanges or quick-connect fittings. The
gaskets should be constructed of virgin Viton B materials. The user should
have a hose-management program in
place to ensure the integrity of hoses.
All hoses must be dedicated to sulfuric
acid service. [9]
Following the guidelines presented in
this article will help enable engineers to
safely approach the storage and handling of sulfuric acid.

Edited by Mary Page Bailey

References
1. U.S. Chemical Safety and Hazard Investigation Board
(CSB), Investigation Report Refinery Incident,
Motiva Enterprises LLC, Delaware City Refinery,
July 17, 2001.
2. National Association of Corrosion Engineers,
NACE Standard RP 0294-94, Design, Fabrication and Inspection of Tanks for the Storage of
Concentrated Sulfuric Acid and Oleum at Ambient
Temperatures, 2006.
3. American Petroleum Institute, API 653 Tank Inspection, Repair, Alteration and Reconstruction,
November 2014.
4. McKetta, J.J., Encyclopedia of Chemical Processing and
Design, CRC Press, June 1995.
5. American Petroleum Institute, API 2000 Venting Atmospheric and Low-Pressure Storage Tanks, 7th Ed.,
March 2014.
6. American Petroleum Institute, API RP 2009 Safe Welding, Cutting and Hot Work Practices in the Petroleum and
Petrochemical Industries, February 2002.
7. American Petroleum Institute, API 570 Piping Inspection Code, November 2009.
8. NorFalco LLC, Sulfuric Acid Handbook, www.
myh2so4.norfalco.com/documents/NorFalco_
H2SO4TechBrochure.pdf, 2007.
9. DuPont Clean Technologies, Equipment Related Frequently
Asked Questions, www2.dupont.com/Clean_Technologies/es_MX/assets/downloads/Equipment_FAQs.pdf.

Author
Koya Venkata Reddy is senior manager, process engineering at FACT Engineering & Design Organization
(FEDO), a division of Fertilizers And
Chemicals Travancore Ltd. (FACT;
Udyogamandal
683501,
Kochi,
Kerala, India; Phone: 91-484-2568763
Email: koyareddy@yahoo.com). He has
24 years of experience in chemical
plant operations, including expertise in
the fields of process control, process design, process risk
analysis, HAZOP, process simulations, environmental management and plant revamps. He is a recipient of FACTs Merit
Award. Reddy holds a Bachelor of Technology degree from
Andhra University, Visakhapatnam and a Master of Technology degree in project management from Cochin University of
Science and Technology. He also received an M.B.A. in finance from Indira Gandhi National Open University (IGNOU),
Delhi. He is a lifetime member of the Indian Institute of Chemical Engineers (IIChE) and a member of the Institution
of Engineers (India).

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